WO2013157376A1 - Élément en alliage de magnésium et procédé de fabrication correspondant - Google Patents
Élément en alliage de magnésium et procédé de fabrication correspondant Download PDFInfo
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- WO2013157376A1 WO2013157376A1 PCT/JP2013/059684 JP2013059684W WO2013157376A1 WO 2013157376 A1 WO2013157376 A1 WO 2013157376A1 JP 2013059684 W JP2013059684 W JP 2013059684W WO 2013157376 A1 WO2013157376 A1 WO 2013157376A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/001—Extruding metal; Impact extrusion to improve the material properties, e.g. lateral extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/005—Continuous extrusion starting from solid state material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/01—Continuous casting of metals, i.e. casting in indefinite lengths without moulds, e.g. on molten surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/06—Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0408—Light metal alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
Definitions
- the present invention relates to a magnesium alloy member suitable for use in products in which bending stress and / or torsional stress mainly acts and a method for manufacturing the same.
- Patent Document 1 discloses that a solid product is produced from a molten metal of Mg—Al—Zn—Mn—Ca—RE (rare earth element) by wheel casting, and the solid product is consolidated by drawing.
- Mg—Al—Zn—Mn—Ca—RE rare earth element
- Patent Document 2 discloses Mg—X—Ln (X is one or more of Cu, Ni, Sn, and Zn, and Ln is one or more of Y, La, Ce, Nd, and Sm).
- X is one or more of Cu, Ni, Sn, and Zn
- Ln is one or more of Y, La, Ce, Nd, and Sm.
- Patent Document 3 discloses a technique for obtaining a magnesium alloy wire having a tensile strength of 250 MPa or more and an elongation of 6% or more by drawing a cast or extruded material of Mg—Al—Mn alloy.
- the techniques disclosed in these patent documents are effective for increasing the strength of magnesium alloys.
- the magnesium alloy disclosed in Patent Document 1 is not sufficient in mechanical properties to satisfy market demand as a strength component.
- the strength of magnesium alloy wire that can be reduced in weight while maintaining the same size as current steel springs is According to the inventors' calculations, 0.2% proof stress of 550 MPa or more is required inside the wire, and 0.2% proof stress of 650 MPa or more is required near the surface of the wire. Further, in order to form a coil spring or the like, at least 5% or more elongation is required inside the wire.
- the highest strength 0.2% proof stress alloy member disclosed in Patent Document 1 has a low ductility and only 1.6% elongation.
- the elongation of the alloy member having the most excellent ductility disclosed in Patent Document 1 is 4.7%, and has an elongation close to the value desired in the present invention, but the strength is 0.8.
- the 2% proof stress is poor at 535 MPa, and the requirements cannot be satisfied.
- Patent Document 2 a hardness of 170 HV or more is obtained. According to a trial calculation by the present inventors, this hardness is a hardness corresponding to a 0.2% proof stress of 650 MPa or more on the surface of the wire.
- Patent Document 2 does not disclose any characteristics indicating ductility.
- the magnesium alloy disclosed in Patent Document 2 contains a large amount of rare earth elements and is composed of an amorphous phase of 50% or more, so its ductility is very poor, and it is easily assumed that sufficient elongation cannot be obtained. .
- the amorphous phase is thermally unstable and has a drawback that it easily crystallizes due to external factors such as environmental temperature. Since mixed phase alloys of amorphous phase and crystalline phase differ greatly depending on the ratio of the phases, it is difficult to stably produce products with uniform characteristics in production, and the quality assurance in the market is difficult. However, application to industrial products is inappropriate.
- the magnesium alloy disclosed in Patent Document 3 has a sufficient ductility with an elongation of 6% or more. However, the tensile strength is 479 MPa at the maximum, and the above 0.2% proof stress of 550 MPa or more cannot be satisfied inside the wire.
- the conventional magnesium alloy does not satisfy both the 0.2% proof stress and the elongation required when assuming a strength component (for example, a spring) in which bending stress and / or torsional stress mainly acts.
- the fatigue strength was also insufficient.
- the present invention satisfies both the properties having a trade-off relationship of 0.2% proof stress and elongation, thereby providing strength and formability (hereinafter, unless required otherwise, ductility necessary for bending processing, coiling processing, etc.).
- the present invention provides a magnesium alloy member suitable for use in a product that is superior in meaning), has a high surface strength and a large surface compressive residual stress, and which is mainly subjected to bending stress and / or torsional stress, and a method for manufacturing the same. It is an object.
- the present invention is a member made of a magnesium alloy wire used for a member on which bending stress and / or torsional stress mainly acts, and has a portion having a maximum hardness of 170 HV or more near the surface of the wire, It has a 0.2% proof stress of 550 MPa or more and an elongation of 5% or more, and the maximum compressive residual stress in the vicinity of the wire surface is 50 MPa or more.
- the present invention is a member made of a magnesium alloy wire used for a member on which bending stress and / or torsional stress mainly acts, and has a portion having a maximum hardness of 170 HV or more in the vicinity of the surface of the wire.
- Depth from the surface of the wire that has a 0.2% proof stress of 550 MPa or more and an elongation of 5% or more inside the wire, and further, the value of the compressive residual stress in the residual stress distribution in the depth direction from the surface of the wire is zero.
- Is the crossing point the integral value I ⁇ R of the compressive residual stress in the region from the surface of the wire to the crossing point is 7 MPa ⁇ mm or more.
- the vicinity of the wire surface of the member indicates a range from the outermost surface of the member to about d / 10 (d is the diameter of the wire), and has a maximum hardness of 170 HV or more in the vicinity of the wire surface.
- 0.2% proof stress of 650 MPa or more is satisfied in the vicinity of the wire surface of the member.
- the yield stress that is, 0.2% proof stress
- the present invention since it has a high strength and high ductility region inside the wire and a further high strength region in the vicinity of the surface of the wire, the characteristics in a trade-off relationship of 0.2% proof stress and elongation, Satisfaction can be achieved by having an appropriate distribution of mechanical properties for a part on which bending stress and / or torsional stress mainly acts. Furthermore, since the maximum compressive residual stress is sufficiently high at 50 MPa or more in the vicinity of the surface of the wire, the generation of cracks starting from the outermost surface of the wire of the member can be suppressed, and the fatigue resistance is improved.
- compressive residual stress can be applied by shot peening, and since the yield stress near the surface of the wire is high, such a large compressive residual stress can be obtained. If the maximum compressive residual stress in the vicinity of the surface of the wire is less than 50 MPa, it is difficult to obtain sufficient fatigue strength. The maximum compressive residual stress in the vicinity of the wire surface is more preferably 100 MPa or more.
- the integral value I ⁇ R of the compressive residual stress in the region from the surface of the member to the crossing point is 7 MPa ⁇ mm or more, not only the surface of the member but also the inside of the wire is greatly compressed. Residual stress is applied, and not only the surface of the wire of the member but also the generation of cracks starting from the inside of the wire can be effectively suppressed. If the integral value I ⁇ R of the compressive residual stress is less than 7 MPa ⁇ mm, it is difficult to sufficiently obtain the effect.
- I ⁇ R is preferably 10 MPa ⁇ mm or more, and more preferably 20 MPa ⁇ mm or more.
- the compressive residual stress at a depth of 0.1 mm from the surface of the wire of the member is 50 MPa or more and the crossing point is 0.2 mm or more.
- a member that satisfies this condition is given a large compressive residual stress from the surface of the wire of the member to the deep, so that not only the surface of the member but also the cracks starting from the inside of the wire can be more effectively suppressed. can do.
- the compressive residual stress at a depth of 0.1 mm from the surface of the wire of the member is less than 50 MPa, and the crossing point is less than 0.2 mm, sufficient compressive residual stress is not applied to the inside of the wire of the member, It is difficult to obtain high fatigue strength.
- the compressive residual stress at a depth of 0.1 mm is more preferably 100 MPa or more.
- the magnesium alloy member of the present invention is preferably composed of atomic percent, Ni: 2 to 5%, Y: 2 to 5%, balance: Mg and inevitable impurities. Below, the reason for limitation of a material composition and its numerical value is demonstrated.
- Ni 2-5 atomic%
- Zn has been mainly added as the first additive element for improving the strength and ductility of the magnesium alloy.
- the addition of Zn is insufficient for achieving both high strength and high ductility. Therefore, it is desirable to add Ni as the first additive element.
- Ni has a larger effect on high strength and high ductility than Zn.
- Y 2-5 atomic% Even with the addition of Ni, which greatly contributes to high strength and high ductility, it is not easy to obtain the high strength targeted by the present invention. Therefore, it is desirable to add Y as the second additive element. Addition of Y forms a high-strength Mg—Ni—Y compound phase. Y has a high solubility in Mg and is effective for strengthening solid solution in the ⁇ -Mg phase. In addition, as described later, it is possible to achieve higher strength by combining the starting material with the rapid solidification method.
- Ni is less than 2 atomic% and Y is less than 2 atomic%, the maximum hardness in the vicinity of the surface does not reach sufficient hardness, and for a strength component on which bending stress and / or torsional stress mainly acts The strength is not enough.
- Ni exceeds 5 atomic% and Y exceeds 5 atomic% workability is remarkably deteriorated and breaks during extrusion. This is because the amount of the high hardness compound phase formed by the addition of Ni and Y is increased and the size thereof is coarsened. As a result, the deformation resistance is increased and the toughness is reduced, leading to fracture.
- the magnesium alloy in the present invention is not limited to the composition of three elements of Mg, Ni, and Y.
- the main additive may be Mg, Ni, Y, and a third additive element may be added for the purpose of crystal grain refinement, corrosion resistance improvement, and the like. In that case, for example, Zr or Al is effective.
- the method for producing a magnesium alloy member of the present invention includes a step of producing a starting material in the form of a foil strip, a foil piece, or a thin wire made of a magnesium alloy by a rapid solidification method, and sintering the starting material. Sintering process to form billet by joining, plastic working process to give plastic work material to billet by plastic working, forming plastic work material, and applying compressive residual stress to plastic working material after forming The above-mentioned member is obtained by the step of performing.
- a starting material having the material composition described above in the form of a foil strip, foil piece, or fine wire made of a magnesium alloy by a rapid solidification method.
- a powder with a large specific surface area described as one means in Patent Document 1 or when using an alloy having a more active material composition an instantaneous container after molding of the starting material Processes such as filling and canning are unnecessary.
- a step of producing a fine wire made of a magnesium alloy by a molten metal extraction method a sintering step of forming a billet by joining the thin wire by sintering, and a billet It is charged as it is into the container of the press and the extrusion process is performed on the billet to obtain the extruded material, the extruded material is molded, and the extruded material after molding is subjected to compression residual stress using shot peening treatment.
- the manufacturing method which obtains the said member by the process to do is employable.
- a high strength and high ductility region inside the wire of the member can be obtained, and a further high strength region can be obtained near the surface of the wire of the member.
- the high strength and high ductility zone inside the wire of the member and the further high strength zone near the surface are gradually connected and do not have a clear boundary as a mechanical property. Is particularly preferred. When both regions have clear boundaries, the possibility of the interface becoming the starting point of fracture increases due to the difference in hardness (or elastic strain), but the two regions gradually connect without having a clear boundary. This makes it possible to avoid the danger that the interface becomes a starting point of fracture.
- the process is shortened compared to the case where canning is performed, and the billet can be manufactured at a low cost.
- the magnesium alloy member of the present invention is suitable for vehicle parts such as automobiles, and the diameter of the wire used for the member is preferably 3 to 13 mm in order to satisfy the required specifications.
- the present invention is a spring using a wire having a diameter of 3 to 13 mm.
- the wire of the magnesium alloy member of the present invention has high surface strength and formability. Therefore, by using it for molded parts where bending stress and / or torsional stress mainly acts, it is possible to significantly reduce the weight without enlarging the part size when compared with conventional steel parts. . Specifically, for example, it can be applied to automobile parts such as seat frames that occupy a large weight and springs that require high strength (suspension springs, valve springs, clutch torsion springs, torsion bars, stabilizers), etc. Has excellent strength and formability.
- a starting material of a magnesium alloy consisting of Ni: 2 to 5%, Y: 2 to 5%, balance: Mg and inevitable impurities in atomic% is produced.
- a rapid solidification method such as a single roll method, a melt spinning method, or a molten metal extraction method is used, and a foil strip, a foil piece, or a thin wire is formed.
- the amount of each additive element in the ⁇ -Mg phase in the foil strip, foil piece, or fine wire produced by the rapid solidification method is large. Therefore, even if the addition amount of each element is the same, the strength can be increased by solid solution strengthening. Further, in the rapid solidification method, the crystal grains become fine. Refinement of crystal grains contributes to improvement in strength and also improves ductility, and is effective in improving overall mechanical properties in combination with solid solution strengthening.
- the rapidly solidified powder including the atomizing method which is generally used as a starting material consisting of rapid solidification, is not suitable as the starting material in the present invention.
- Mg is active, an extremely thin oxide film is easily formed on the surface when exposed to the atmosphere.
- the total area of the oxide film is very large as compared with the foil strip, foil piece, or fine wire in the present invention.
- the oxide layer formed on the surface hinders bonding at the contact surface between the powders.
- a large amount of oxide or oxygen decomposed by the oxide is taken into the inside.
- a powder having a large specific surface area is liable to cause poor bonding or embrittlement due to mixing of oxide or oxygen, and the characteristics are deteriorated as compared with the case of using a foil strip, a foil piece, or a fine wire.
- an instantaneous canning process is required after powder molding.
- FIG. 1 shows a schematic configuration of a fine metal wire manufacturing apparatus 100 (hereinafter abbreviated as “apparatus 100”), which is one means for producing a starting material
- apparatus 100 a fine metal wire manufacturing apparatus 100
- FIG. 4B is a cross-sectional view of the peripheral edge 141 a of the rotating disk 141 used in the apparatus 100.
- FIG. 1B is a side cross-sectional view in the direction perpendicular to the paper surface of FIG.
- the apparatus 100 is an apparatus for producing fine metal wires using a molten metal extraction method.
- the upper end portion of the rod-shaped raw material M is melted, and the molten material Ma is brought into contact with the peripheral edge 141a of the rotating disk 141, whereby a part of the molten material Ma is disc-shaped.
- a magnesium alloy fine wire F is formed by drawing out in a substantially tangential direction of the circumference and quenching.
- Mg—Ni—Y based magnesium alloy is used as the raw material M, and for example, a magnesium alloy fine wire F having a wire diameter of 200 ⁇ m or less is manufactured.
- the wire diameter of the magnesium alloy fine wire F is not particularly limited, and can be appropriately selected from the viewpoints of productivity, handleability in subsequent steps, and the like. A sufficient effect can be obtained by setting the wire diameter in the range of 200 ⁇ m or less with respect to the solid solution amount of each additive element in the ⁇ -Mg phase and the refinement of the structure.
- the apparatus 100 includes a chamber 101 that can be sealed, and in the chamber 101, a raw material supply unit 110, a raw material holding unit 120, a heating unit 130, a thin metal wire forming unit 140, a temperature measuring unit 150, A high frequency generator 160 and a thin metal wire recovery unit 170 are provided.
- an inert gas such as an argon gas is used as the atmospheric gas in order to prevent oxygen, nitrogen, and the like from reacting with the molten material Ma.
- the raw material supply unit 110 is provided at the bottom of the chamber 101, for example, and moves the raw material M toward the arrow B direction at a predetermined speed and supplies the raw material M to the raw material holding unit 120.
- the raw material holding unit 120 has a function of preventing the molten material Ma from moving in the radial direction and a guide function of guiding the raw material M to an appropriate position of the thin wire forming unit 140.
- the raw material holding unit 120 is a cylindrical member, and is provided below the disc 141 between the raw material supply unit 110 and the thin metal wire forming unit 140.
- the heating unit 130 is a high-frequency induction coil that generates a magnetic flux for forming the molten material Ma by melting the upper end portion of the raw material M.
- the material of the raw material holding unit 120 is preferably a material that does not react with the molten material Ma. As a practical material of the raw material holding unit 120, for example, graphite is suitable.
- the metal fine wire forming unit 140 forms the magnesium alloy fine wire F from the molten material Ma using the disc 141 rotating around the rotation shaft 142.
- the disc 141 is made of, for example, copper or copper alloy having high thermal conductivity. As shown in FIG. 1B, a V-shaped peripheral edge 141 a is formed on the outer periphery of the disc 141.
- the temperature measuring unit 150 measures the temperature of the molten material Ma.
- the high frequency generator 160 supplies a high frequency current to the heating unit 130.
- the output of the high frequency generator 160 is adjusted based on the temperature of the molten material Ma measured by the temperature measuring unit 150, and the temperature of the molten material Ma is kept constant.
- the fine metal wire collecting unit 170 accommodates the fine metal wire F formed by the fine metal wire forming unit 140.
- the raw material supply unit 110 continuously moves the raw material M in the direction of the arrow B and supplies the raw material M to the raw material holding unit 120.
- the heating unit 130 melts the upper end portion of the raw material M by induction heating to form the molten material Ma.
- the molten material Ma is continuously fed toward the peripheral edge 141a of the disk 141 rotating in the direction of arrow A, and the molten material Ma contacts the peripheral edge 141a of the disk 141, and a part of the circular disk 141 141 is drawn in a substantially tangential direction of the circumference of the circumference, and is rapidly cooled to form a magnesium alloy fine wire F.
- the magnesium alloy fine wire F thus formed extends in a substantially tangential direction of the circumference of the disc 141 and is accommodated by the metal fine wire collecting portion 170 located at the tip thereof.
- the produced starting material is formed into a billet for plastic working by sintering.
- a sintering method atmospheric sintering, vacuum sintering, discharge plasma sintering, or the like can be used, and the sintering can be performed by no pressure or pressure sintering.
- the properties and quality of the billet after sintering affect the properties and quality of the product subjected to plastic working. Therefore, vacuum hot press (HP) that has a pressurization mechanism and can be sintered in a vacuum or inert gas atmosphere to form a dense billet with higher cleanliness, uniform structure and fewer pores Sintering by is preferred.
- HP vacuum hot press
- a heating chamber is arranged inside a vacuum vessel, and a mold is arranged inside the heating chamber, and a press ram protruding from a cylinder provided on the upper side of the vacuum vessel moves up and down in the heating chamber.
- the upper punch attached to the press ram is inserted into the mold.
- the HP mold thus configured is filled with a magnesium alloy fine wire F as a starting material, and the inside of the vacuum vessel is made a vacuum or an inert gas atmosphere and the temperature is raised to a predetermined sintering temperature. And the magnesium alloy fine wire F is pressurized and sintered by the upper punch inserted into the mold.
- the heating temperature is preferably 350 ° C. or higher. .
- the heating temperature exceeds 500 degreeC, sintering in the contact of fine wires fully progresses, and there are almost no pores.
- the heating temperature exceeds 500 ° C., the structure becomes coarse, and a fine structure cannot be obtained even if the product reaches a product after the subsequent plastic working process. As a result, it becomes difficult to obtain a magnesium alloy wire with sufficient strength, and therefore the heating temperature is preferably 500 ° C. or lower.
- the starting material is powder
- a series of apparatuses for providing a vacuum or an inert atmosphere becomes large, it is not easy to uniformly fill a mold or a metal sheath with powder in a closed apparatus. Production becomes difficult.
- canning is required before exposure to the atmosphere, and the sintered body in the metal sheath is insufficiently sintered between the powders, and there are many pores and density. It becomes a non-uniform sintered body.
- the metal sheath is removed, since there are many pores communicating with the surface, it is inevitable that the interior is exposed to the atmosphere. Therefore, even in the billet state, the metal sheath cannot be removed, and in the next plastic working step, processing with canning is forced.
- Plastic processing The processing from billet to wire is performed by plastic processing including drawing, rolling, extrusion, and forging as warm processing.
- Plastic processing at an appropriate temperature and degree of processing (cross-sectional reduction rate) is effective in increasing the strength of magnesium alloys because of the refinement of the structure and work hardening caused by dynamic recrystallization.
- drawing or extrusion is more preferable for a wire rod on which bending stress and / or torsional stress mainly acts.
- a uniform cross-sectional shape indispensable as a wire can be obtained, and larger strain can be introduced into the surface of the wire as compared with the inside.
- the structure in the vicinity of the surface of the wire becomes finer, and the strength on the surface can be further increased in addition to the characteristics inside the wire.
- the billet is made of a casting, it is not possible to increase the strength even with a magnesium alloy having a composition equivalent to that of the present invention. This is because in the casting, the original ⁇ -Mg phase crystal grains are coarse, and the precipitated compound phase is also coarse. Therefore, a combination of high deformation resistance and large accumulation of strain results in a fine structure. This is because it leads to shear fracture before. In addition, since the amount of the additive element dissolved in the ⁇ -Mg phase is small, the effect of increasing the strength by solid solution strengthening of the ⁇ -Mg phase is also poor.
- the sintered structure is also fine, so that deformation resistance Is small. Therefore, because of its excellent deformability, it becomes possible to introduce a large strain at a lower temperature in plastic processing and to accumulate a large amount of internal energy as a driving force for recrystallization, so that a finer structure can be obtained. . Further, since the amount of the additive element added to the ⁇ -Mg phase is large, the effect of solid solution strengthening is great, and the strength is increased in combination with the microstructure.
- FIG. 2 is a diagram showing an extrusion apparatus 200 used when an extrusion process is adopted as the plastic process.
- reference numeral 205 denotes an outer mold
- reference numeral 210 denotes a container accommodated in the outer mold 205.
- the container 210 has a cylindrical shape, and a lower mold 220 is coaxially disposed on one end face side thereof.
- a die 230 is disposed between the container 210 and the lower mold 220.
- a punch 240 is slidably inserted into the container 210.
- a heater 260 is disposed on the outer periphery of the container 210.
- the punch 240 is lowered and the billet B is compressed.
- the compressed billet B is extruded into the space in the lower mold 220 while being reduced in diameter by the die 230 to form a wire.
- Extrusion by the above-described extruder is preferably performed at a billet B heating temperature of 315 to 335 ° C., an extrusion ratio of 5 to 13, and a forward speed of the punch 240 of 2.5 mm / second or less. Under these conditions, refinement of the structure by induction of dynamic recrystallization and work hardening by introducing strain are appropriate, and the inside of the wire has high strength and high ductility, and a plastic work material with higher strength near the wire surface is formed. Is done.
- the maximum hardness in the vicinity of the surface of the wire of the member is 170 HV or more
- the inside of the wire has a 0.2% yield strength of 550 MPa or more and an elongation of 5% or more
- bending stress and / or torsional stress mainly acts.
- a plastic working material suitable for strength parts can be obtained.
- the heating temperature of billet B is less than 315 ° C.
- the deformation resistance is large, and thus the extrusion process is difficult, and breakage during the extrusion process and the occurrence of rough skin and cracks on the surface of the wire are caused.
- the wire material has been increased in strength, but the ductility is impaired, and the elongation of 5% or more necessary for formability cannot be obtained.
- the heating temperature exceeds 335 ° C., it is difficult to sufficiently obtain the effect of refining the structure by dynamic recrystallization and the work hardening effect by introducing strain. As a result, it is difficult to obtain sufficient hardness in the vicinity of the wire surface of the member.
- the conditions in the extrusion process are not limited to the values in the above-mentioned range and the examples described later, but the high strength and high ductility inside the wire of the member and further increase in strength near the surface of the wire. It should be set within an appropriate range with a focus on securing.
- the introduction of strain and the induction of dynamic recrystallization in plastic processing are influenced by complicated relationships such as material composition, processing rate, processing temperature, etc., and are guided by setting conditions appropriately by theory, experience, and experiment. Is.
- the average crystal grain size of the ⁇ -Mg phase measured by the EBSD method in the portion having the highest hardness in the vicinity of the surface of the wire of the plastic working material is desirably 1 ⁇ m or less. It is well known that the refinement of crystal grains, such as the Hall Petch rule, greatly contributes to the increase in strength. In addition, the grain refinement is effective in suppressing the initial crack initiation on the surface of fatigue parts subjected to repeated stress. Is effective.
- the average crystal grain size of the ⁇ -Mg phase in the vicinity of the surface is very fine as 1 ⁇ m or less, and not only the static strength It is also suitable for fatigue resistance.
- the plastic work material may be molded into a desired product shape. For example, you may shape
- a shot peening process is performed on the molded plastic work material to give a compressive residual stress.
- the shot peening treatment is desirably performed with an average shot size of 0.01 to 0.5 mm and a projection pressure of 0.1 to 0.5 MPa.
- the shot material is not particularly limited, but is preferably a material harder than the workpiece.
- the maximum surface roughness (Rz) of the wire after shot peening is desirably 20 ⁇ m or less. When the maximum surface roughness exceeds 20 ⁇ m, fatigue failure starting from the surface tends to occur.
- shot peening conditions such as shot size, projection pressure, and projection time are not limited to the above, and may be adjusted according to a desired compressive residual stress distribution.
- the magnesium alloy member of the present invention is manufactured through the above steps. Since the hardness of the member in the vicinity of the wire surface is high, a compressive residual stress can be effectively applied, and the maximum compressive residual stress in the vicinity of the wire surface is 50 MPa or more. Further, the integral value I- ⁇ R of the compressive residual stress in the region from the surface of the member to the crossing point is 7 MPa ⁇ mm or more. Further, the compressive residual stress at a depth of 0.1 mm from the surface of the wire of the member is 50 MPa or more, and the crossing point is 0.2 mm or more. Since such a large and deep compressive residual stress is applied, the fatigue resistance is excellent.
- each element raw material for producing castings was weighed so as to have a desired magnesium alloy component in accordance with a predetermined casting size, and a casting was produced by vacuum melting using each element raw material.
- Table 1 shows the components of the casting.
- a graphite crucible and a copper alloy mold were used.
- a thin wire was formed by a molten metal extraction method using the apparatus 100 shown in FIG.
- a thin wire having an average wire diameter of 60 ⁇ m was formed in an inert atmosphere by Ar gas replacement using a graphite raw material holding part and a copper alloy disc.
- the formed thin wire was filled in a graphite sintering mold as it was without canning, and sintered by HP to produce a billet having a diameter of 15 mm and a length of 50 mm, and a billet having a diameter of 33 mm and a length of 50 mm. .
- Sintering with HP was performed at an sintering atmosphere of 300 to 525 ° C. and a pressing pressure of 50 MPa under an inert atmosphere (atmospheric pressure 0.08 MPa) with Ar gas replacement.
- the produced billet was processed into a wire using the extrusion apparatus 200 shown in FIG. Specifically, a graphite-based lubricant (OILDAG-E manufactured by Nippon Atchison Co., Ltd.) is used, the extrusion ratio is 3 to 15, the extrusion speed (the advance speed of the punch 240) is 0.01 to 5 mm / second, and are also shown in Table 1.
- a graphite-based lubricant (OILDAG-E manufactured by Nippon Atchison Co., Ltd.) is used, the extrusion ratio is 3 to 15, the extrusion speed (the advance speed of the punch 240) is 0.01 to 5 mm / second, and are also shown in Table 1.
- the extrusion temperature is in the range of 300 to 425 ° C.
- a container 210 having an inner diameter of 16 mm and a die 230 having a hole diameter of 5 mm are used for a billet having a diameter of 15 mm (extrusion ratio 10)
- a container 210 having an inner diameter of 35 mm is used for a billet having a diameter of 33 mm.
- a hole diameter of 20 mm (extrusion ratio of 3) a hole diameter of 15.5 mm (extrusion ratio of 5), a hole diameter of 11 mm (extrusion ratio of 10), a hole diameter of 9.7 mm (extrusion ratio of 13), and a hole diameter of 9 mm (extrusion ratio of 15).
- Each of the dies 230 was used to produce a wire (No. 1 to 30).
- a cast billet was also extruded to produce a wire (No. 31 to 33).
- a commercially available magnesium alloy AZ31 having a diameter of 5 mm was also prepared (No. 34).
- the “billet form” represents the manufacturing method up to the billet before extrusion
- the “fine wire sintered body” is a billet produced by sintering fine wires
- the “cast” is the raw material casting. Show billets as they are.
- Table 1 also shows the extrusion results.
- “X” indicates that the wire was not obtained after extrusion after being broken during extrusion
- “ ⁇ ” indicates that the wire was obtained, but the surface was visually checked for rough skin and cracks.
- “” Indicates that a good wire material without rough skin and cracks was obtained.
- a tensile test was performed on each wire.
- a test piece with a parallel part diameter of 1.6 mm was produced by machining from a wire with a diameter of 5 mm, and a test piece with a parallel part diameter of 3 mm was produced by machining from a wire with a diameter of 9 mm or more.
- a universal material testing machine manufactured by Instron, model number 5586 was used for each test piece, and a tensile test was performed at a test speed of 0.5 mm / min at room temperature. From the tensile test results, 0.2% yield strength and elongation were determined.
- the hardness of the wire resin embedding is performed so that the cross section of the extruded wire is exposed, mirror polishing is performed by mechanical polishing, a test piece is prepared, and a Vickers hardness tester (Future Tech, FM-600) is prepared. ) was used for measurement. At this time, the radial distribution in the cross section of the extruded material was measured at a test load of 25 gf, and the center part hardness and the surface layer part maximum hardness were determined.
- the above measurement was performed after the entire surface of the wire was chemically polished using a mixed solution of nitric acid and hydrochloric acid with respect to the wire, and the residual stress distribution in the depth direction was obtained by repeating this, and from the result, 0.1 mm from the surface was obtained.
- the compressive residual stress distribution at the depth and the crossing point CP were determined.
- the compressive residual stress integral value I- ⁇ R was calculated by integrating the compressive residual stress from the surface to the crossing point in the relationship diagram of depth and residual stress. As an example, no.
- the residual stress distribution of the sample No. 7 is shown in FIG.
- the average crystal grain size of the ⁇ -Mg phase in the vicinity of the wire surface was measured.
- the average crystal grain size of the ⁇ -Mg phase was measured by using the EBSD method (FESMEM (Field Emission Scanning Electron Microscope, JEOL: JSM-7000F)) using the specimen used for the hardness test as it is ( At the position where the highest hardness was obtained in the vicinity of the surface in the cross section of the wire extruded with an electron beam backscattering diffractometer (manufactured by TSL), the analysis example was 10,000 times the comparative example (No. .33, 34) were measured at an analysis magnification of 2,000.
- FESMEM Field Emission Scanning Electron Microscope, JEOL: JSM-7000F
- the maximum hardness in the vicinity of the surface of the wire is 170 HV or more
- the internal 0.2% proof stress is 550 MPa or more
- the elongation is 5.0% or more
- the compressive residual stress at 0.1 mm from the surface is 50 MPa or more
- I The examples of the present invention (Nos. 4 to 8, 14, 15, 17 to 19, 21, 24 to 29) have a - ⁇ R of 7 MPa ⁇ mm or more. Compared with comparative examples (Nos.
- the strength of the examples of the present invention is remarkably high, and the inside of the wire has a 0.2% proof stress of 551 MPa or more, and It has a high strength and high ductility region with an elongation of 5% or more.
- the maximum hardness is 170 HV or more, and it has a further high strength region that satisfies 0.2% proof stress of 650 MPa or more.
- the internal high strength and high ductility region and the further high strength region in the vicinity of the surface are gradually connected to each other and do not have a clear boundary. As a whole, the wire has excellent strength and toughness and has sufficient formability. is doing.
- the compressive residual stress on the outermost surface is large, the compressive residual stress at a depth of 0.1 mm from the surface is 170 MPa or more, and the compressive residual stress in the vicinity of the surface is large. Furthermore, a large compressive residual stress is obtained from the surface of the wire to the inside, with CP of 0.2 mm or more and I ⁇ R of 27 MPa ⁇ mm or more. Therefore, even when bending stress and / or torsional stress is applied, high fatigue strength can be obtained.
- the average crystal grain size of the ⁇ -Mg phase is 0.19 to 0.76 ⁇ m. It is extremely fine compared to 6.76 and 8.75 ⁇ m of 33 and 34 samples. It is clear that these fine crystal grains contribute to the improvement of the hardness near the surface.
- the sample No. 7 has a deep and large compressive residual stress.
- the projection pressure is in the range of 0.1 to 0.5 MPa, it is 50 MPa or more at a depth of 0.1 mm from the surface, CP is 0.2 mm or more, I- ⁇ R is 7 MPa ⁇ mm or more, surface roughness High fatigue strength can be obtained while suppressing the thickness Rz to 20 ⁇ m or less.
- the wire material was obtained by performing shot peening on the plastic work material, but after forming the plastic work material into a desired product shape, it is possible to apply compressive residual stress by shot peening treatment. In this case, the same effect as described above can be obtained.
- the magnesium alloy wire of the present invention is suitable for high-strength parts on which bending stress and / or torsional stress mainly acts.
- a member made of the magnesium alloy wire of the present invention it is possible to significantly reduce the weight without substantially increasing the size of the component when compared with a conventional steel component.
- the weight reduction effect is great in a seat frame that occupies a large weight ratio or a spring (suspension spring, valve spring, clutch torsion spring, torsion bar, stabilizer) that requires high strength.
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Abstract
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CN201380020508.1A CN104245982B (zh) | 2012-04-18 | 2013-03-29 | 镁合金部件及其制造方法 |
EP13778444.3A EP2840155B1 (fr) | 2012-04-18 | 2013-03-29 | Élément en alliage de magnésium et procédé de fabrication correspondant |
US14/395,121 US9920403B2 (en) | 2012-04-18 | 2013-03-29 | Magnesium alloy member and production method therefor |
ES13778444.3T ES2654619T3 (es) | 2012-04-18 | 2013-03-29 | Elemento de aleación de magnesio y procedimiento para su fabricación |
KR1020147030849A KR101659199B1 (ko) | 2012-04-18 | 2013-03-29 | 마그네슘 합금 부재 및 그 제조 방법 |
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JP2012094985A JP5948124B2 (ja) | 2012-04-18 | 2012-04-18 | マグネシウム合金部材及びその製造方法 |
JP2012-094985 | 2012-04-18 |
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PCT/JP2013/059684 WO2013157376A1 (fr) | 2012-04-18 | 2013-03-29 | Élément en alliage de magnésium et procédé de fabrication correspondant |
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US (1) | US9920403B2 (fr) |
EP (1) | EP2840155B1 (fr) |
JP (1) | JP5948124B2 (fr) |
KR (1) | KR101659199B1 (fr) |
CN (1) | CN104245982B (fr) |
ES (1) | ES2654619T3 (fr) |
WO (1) | WO2013157376A1 (fr) |
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CN106086563A (zh) * | 2016-08-05 | 2016-11-09 | 沈阳明腾科技有限公司 | 一种高强耐热铸造镁合金及其制备方法 |
JP7370167B2 (ja) * | 2018-04-25 | 2023-10-27 | 東邦金属株式会社 | マグネシウム合金のワイヤ及びその製造方法 |
JP7370166B2 (ja) * | 2018-04-25 | 2023-10-27 | 東邦金属株式会社 | マグネシウム合金のワイヤ及びその製造方法 |
CN113118458B (zh) * | 2021-04-20 | 2023-04-07 | 江西省科学院应用物理研究所 | 一种激光选区熔化成形金属构件拉伸性能的预测方法 |
CN114622109A (zh) * | 2022-03-14 | 2022-06-14 | 中南大学 | 快速凝固和挤压成型制备医用耐腐蚀镁锌锰合金的方法 |
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JPH0310041A (ja) | 1988-09-05 | 1991-01-17 | Takeshi Masumoto | 高力マグネシウム基合金 |
JPH0390530A (ja) | 1989-08-24 | 1991-04-16 | Pechiney Electrometall | 機械的強度の高いマグネシウム合金及び該合金の急速凝固による製造方法 |
JPH0570880A (ja) * | 1991-09-13 | 1993-03-23 | Takeshi Masumoto | 高強度高靭性マグネシウム合金材料およびその製造方法 |
JPH06316740A (ja) * | 1992-11-13 | 1994-11-15 | Toyota Motor Corp | 高強度マグネシウム基合金およびその製造方法 |
JP2003293069A (ja) | 2001-06-05 | 2003-10-15 | Sumitomo Denko Steel Wire Kk | マグネシウム基合金ワイヤおよびその製造方法 |
WO2007111342A1 (fr) * | 2006-03-20 | 2007-10-04 | National University Corporation Kumamoto University | Alliage de magnesium haute resistance et haute tenacite et procede de production de celui-ci |
JP2012087327A (ja) * | 2010-10-15 | 2012-05-10 | Nhk Spring Co Ltd | 高強度マグネシウム合金線材及びその製造方法、高強度マグネシウム合金部品、並びに高強度マグネシウム合金ばね |
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NZ230311A (en) | 1988-09-05 | 1990-09-26 | Masumoto Tsuyoshi | High strength magnesium based alloy |
JP2511526B2 (ja) * | 1989-07-13 | 1996-06-26 | ワイケイケイ株式会社 | 高力マグネシウム基合金 |
US5221376A (en) * | 1990-06-13 | 1993-06-22 | Tsuyoshi Masumoto | High strength magnesium-based alloys |
JP2807374B2 (ja) * | 1992-04-30 | 1998-10-08 | ワイケイケイ株式会社 | 高強度マグネシウム基合金およびその集成固化材 |
JP2005070880A (ja) * | 2003-08-28 | 2005-03-17 | Casio Comput Co Ltd | 増減表表示制御装置及びプログラム |
US8016955B2 (en) * | 2004-06-14 | 2011-09-13 | Yonsei University | Magnesium based amorphous alloy having improved glass forming ability and ductility |
JP4927899B2 (ja) * | 2009-03-25 | 2012-05-09 | 日本発條株式会社 | ばね用鋼およびその製造方法並びにばね |
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2012
- 2012-04-18 JP JP2012094985A patent/JP5948124B2/ja not_active Expired - Fee Related
-
2013
- 2013-03-29 WO PCT/JP2013/059684 patent/WO2013157376A1/fr active Application Filing
- 2013-03-29 CN CN201380020508.1A patent/CN104245982B/zh not_active Expired - Fee Related
- 2013-03-29 ES ES13778444.3T patent/ES2654619T3/es active Active
- 2013-03-29 KR KR1020147030849A patent/KR101659199B1/ko active IP Right Grant
- 2013-03-29 EP EP13778444.3A patent/EP2840155B1/fr not_active Not-in-force
- 2013-03-29 US US14/395,121 patent/US9920403B2/en not_active Expired - Fee Related
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JPH0310041A (ja) | 1988-09-05 | 1991-01-17 | Takeshi Masumoto | 高力マグネシウム基合金 |
JPH0390530A (ja) | 1989-08-24 | 1991-04-16 | Pechiney Electrometall | 機械的強度の高いマグネシウム合金及び該合金の急速凝固による製造方法 |
JPH0570880A (ja) * | 1991-09-13 | 1993-03-23 | Takeshi Masumoto | 高強度高靭性マグネシウム合金材料およびその製造方法 |
JPH06316740A (ja) * | 1992-11-13 | 1994-11-15 | Toyota Motor Corp | 高強度マグネシウム基合金およびその製造方法 |
JP2003293069A (ja) | 2001-06-05 | 2003-10-15 | Sumitomo Denko Steel Wire Kk | マグネシウム基合金ワイヤおよびその製造方法 |
WO2007111342A1 (fr) * | 2006-03-20 | 2007-10-04 | National University Corporation Kumamoto University | Alliage de magnesium haute resistance et haute tenacite et procede de production de celui-ci |
JP2012087327A (ja) * | 2010-10-15 | 2012-05-10 | Nhk Spring Co Ltd | 高強度マグネシウム合金線材及びその製造方法、高強度マグネシウム合金部品、並びに高強度マグネシウム合金ばね |
Also Published As
Publication number | Publication date |
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JP2013221201A (ja) | 2013-10-28 |
US20150104669A1 (en) | 2015-04-16 |
CN104245982A (zh) | 2014-12-24 |
EP2840155A4 (fr) | 2016-01-20 |
ES2654619T3 (es) | 2018-02-14 |
KR20140143219A (ko) | 2014-12-15 |
JP5948124B2 (ja) | 2016-07-06 |
US9920403B2 (en) | 2018-03-20 |
KR101659199B1 (ko) | 2016-09-22 |
EP2840155A1 (fr) | 2015-02-25 |
CN104245982B (zh) | 2017-06-09 |
EP2840155B1 (fr) | 2017-10-11 |
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